Interpolymers of a methylene malonic ester and an unsaturated alkyd resin



Patented July 9, 1 946 I T OFFICE INTERPOLYMERS OF A I. METHYLENE MALONIC ESTER AND AN UNSATU- RATED ALKYD RESIN r Gaetano F. DAlelio, Pittsfield, Mass., assignor to General Electric Company, a corporation of New York No Drawing. Original application November 16,

1939, Serial No.

now Patent No.

' 2,330,033, dated September 21, 1943. Divided and this application April 30, 1943, Serial 17 Claims. (01, 260-42) This application is a division of my copending application Serial No. 304,783, filed November 16, 1939 now Patent No. 2,330,033, issued September 21, 1943, and assigned to the same assignee asthe present invention. v

This invention relates to the production of organic plastic masses havingvaluable and characteristic properties that make them especially suitable for use in industry, for example in molding, laminating, casting, coating and adhesive applications, and for other purposes. The invention is concerned more particularly with compositions of matter comprising an interpolymer (copolymer) of ingredients comprising a methylene malonic ester and another polymerizable organic compound,'specifically 'a, polymerizable unsaturated alkyd resin obtained by reaction of ingredients comprising a polyhydric alcohol and an alpha unsaturated alpha beta polycarboxylic acid.

The invention claimed in my parent application Serial No. 304,783 is based on my discovery that improved yields of methylene malonic esters, more particularly yields of the order of 30 per cent and higher, can'be obtained by reacting (condensing) a malonic ester with formaldehyde in the ratio. of one mol of the former to at least one mol of the latter and under alkaline conditions to form a methylol derivative, acidifying the mass, dehydrating the acidified mass to obtain a composition comprising a. methylene malonic ester, and separating themethylene malonic ester, as by distillation, from the said composition. The general reaction may be written graphically as'follows: I

COOR

in th above equations n represents an aliphatic,

V or aromatic hydrocarbon radical such as methyl,

ethyl, propyl, isopropyl, butyl, amyl, hexyl, octyl, allyl, methallyl, crotyl, phenyl, cyclohexyl, methoxyethyl, etc. 7

By the above method I have been able to obtain not only methylene dimethyl and methylene diethyl malonates, but also other esters of methylene malonic acid. These esters are useful not only in themselves but I have found that they are particularly adapted for the production of new and useful copolymers.

Illustrative examples of some of th methylene malonic esters that may be prepared and used in practicing the present invention are methylene dimethyl malonate, methylene diethyl malonate, methylene dipropyl malonate, methylene di-iso- .propyl malonate, methylene dibutyl malonate, methylene di-(secondary amyl) malonate, methylene di-(secondary butyl carbinyl) malonate, methylene di-(diethyl carbinyl) malonate, etc.

Other examples will be apparent from the illustrative examplesof radicals that R in the above formulas may represent.

V Illustrative examples of some of the malonic esters, many of Which are new, which I have prepared and which may be reacted with formaldehyd as above briefly described to obtain substantial yields of the corresponding methylene malonicesters are:

Malonic ester Boiling point at G.

19s: 98.5-99 at 4 mm. pressure. 93-95 at 12 mm. pressure.

-166 at 6 mm. pressure. 123-137 at 4 mm. pressure.

Oetyl malonate 188-193 at 4.5 mm. pressure. Allyl malonate 118-122 at 10 mm. pressure. Alpha-ethyl hexyl malonate 160-195 at 4.5 mm. pressure. Isobutyl carbinyl malonate 143-146 at 4 mm. pressure.

Secondary butyl carbinyl malonate- Diethyl carbinyl malonate Methyl propyl carbinyl malonat Ethoxy ethyl malonate Butoxy ethyl malonate. Methoxy ethyl malouate Metltioxy diethylene glycyl malon e. Ethoxy diethylene glycyl malonate. Butoxy diethyleue glycyl malonate.

142-149 at 3.5 mm. pressure.

129-135 at 4 mm. pressure. 119-123 at 4 mm. pressure;

145-149 at 4.5 mm. pressure. -170 at 4.5 mm. pressure. 129.5-130 at 2 mm. pressure. 190-205 at 1.5 mm. pressure.

-187 at 2.0 mm. pressure. 200-222 at 1.5 mm. pressure.

The methylene malonic esters have boiling points only slightly higherthan the corresponding malonic esters, and difler therefrom only within about a 10-degree range.

In producing the organic plastic masses of this invention heat, light, orrheat and light may be used to efifect polymerization, although under such conditions the rate of polymerization is relatively. slow. Hence, to accelerate. the poly-. merization, I prefer to use a catalyst, accompanied by heat, light, or heat and light. Examples of catalysts that may be used are oxygen, ozone, hydrogen peroxide, sulfuric acid, aluminum chloride, boron fluoride, superoxides such as aliphatic acyl peroxides, e. g., acetyl peroxide, stearyl peroxide, etc., peroxides of the aromatic acid series, e. g., benzoyl peroxide; etc. Benzoyl= peroxide is the preferred catalyst because of its' ease of handling, its relative freedom from explosive hazards and its ready solubility in; the. monomeric or partially polymerized: methylene.

Example 1 Parts: Methylene dibutyl malonate 20;.

Poly-hydric alcohol. ester of. an-alpha unsaturated alpha. beta polycarboxylic. acid Benzoyl peroxide NQTE;-This. polyhydric alcohol ester was prepared. by. effecting reaction between equal molar parts of maleic anhydrideand diethylene glycol; The reactants were mixedin, asuitable apparatusv and: thetemperature raised to 200 C, overaperiod of one hour. Heatin was. conti'nued'for six hoursat 200 to 210 0.,

ableresinhaving an acid number of about 27.

The methylene dibutyl malonate was eopolymerized-withthe above-described polyhydrical cohol ester at 90 C., yielding a soft gel at the'end of 40-minutes and a hard copolymerwithintwo hours. andLabrasion-resistant after heating for a total of: 17 hours at 90 C.

Example; 2.

Parts;

Methylene di-isopropyl malonate- Diethylene glycol maleate prepared asdescribed under Example 1. Benzoyl peroxide were treated at 90 C. for 1 hour and 50 minutes.

to givea soft, gel-like copolymer. Continued;

heating for. 1.7. hours at. 90 C.,gave aha-rd 0.0-

polymer.

Example 3 Parts Methylene. di- (secondary amyl).. malonatedu 20 Diethylene glycol maleate prepared as. de.-

scribed, under Example 1.

Benzoyl' peroxide 1 wereheated together at 90 C. for 17 hours to give a hard copolymer.

Example 4 1 7 Parts Methylene dihexyl malonate r, 20

Diethylene glycol maleate prepared as described under Example.I-

Benzoyl' peroxide W 1 were heated at 90 C. for 4 0.minutesto give-a soft gel that became hard within two hours; When at the end of Whichiperiod of,'time therap es-obtaineda. v-iscouS Pour- This copolymer was exceptionally hard ISIS Methylene ('diethylcarbinyl) malonate 4 heated at 90 C. for 17 hours, it was exceptionally hard.

Examplefl Parts Methylene di-(secondary butyl carbinyl) malonate; Diethylene glycol maleate prepared as described under'Example 1, Benzoyl peroxide were'heatedfor 2: hours at C. to give a soft gel, which; became a hard copolymer after 17 hours.

Example 6 Parts 20 Diethylene, glycol maleate prepared as described under Example l. Benzoyl. peroxide were heated for 1 hour and 5 minutes at 90 C. to giveasoft gel: When-.heatedfior; lf'l'hdurs at:90 C; a. hard copolymer Wasformedr Illustrative examples. of other-polyhydric: alco-. hol. esters eof alpha unsaturated. alpha. beta poly... carboxylic acids that may. he-copolymerizediwith. methylene malonic esters to: provide: new: and useful organic; plastic". masses are: ethylene. glycol: maleataztriethylenaglycol maleate, glyceryl mar-1. leate',..ethyl'ene. glycoli fumarate, .diethylene glycol: fumarate; triethylene glycol; fumarata. propylene: lycol. ,fumarate,. glycol;itaconate,v diethylenegly col. itaconate, ,triethylene; glycol; itaoonate, tetrasl ethylene glycol itaconate; glyceryl: itaconate. or: modifications of; these esters. produced by. incor. porating. thereinv nonethylenic: Polybasic: acids. such as the; saturated; aliphatic; acids;. e... g.,v In -Ionic; ucciniautaric, adinici pimelia. 8111-: beria, sebacic... e c.,, t e aroma icmolybasic; acids,- s ch. as. phthalic; in, etrar and; hexa hydrcr phthalic, naphthalinedicarboxylic, eto.-, or mixtures of such acids,

The interpolymersobtained; by, copolymerizing; methylene malonic. esterswith. other polymerizable bodies have awide; range of, properties. Their, hardness and solubilities maybe-varied over. a considerable, range. from. fluid, compositions, of varied; intrinsic viscosity or soft, flexible ,bodiesto ha d; rigid masses. that. can, be swelled or dis-- solved in many volatileand' non-volatile solvents, v ntho e fi'a. hydrocarbonnaturer By suitable. selection, of the, starting monomeric or partly polymerized" material's. interpolymers can be obtained in an insoiuble," infusible statepracti'cally resistantto the destructive-effect of other chemical bodies such as acids, bases, solvents and the like.

Themethylene malonicesterslnay. beconverted; into the: form of interpolymers in molds wither without the application of pressure, in the presence or absence of a material which is a solvent for the. monomer but not for the polymer, or one which isa solvent for both monomer and polymer, or one which is not a solvent for either the monomer or polymer so that spongy or granulatedv polymeric modifications are obtained;

The solid, thermoplastic copolymers of this invention. with or without modifying; agents, may be used in injection, compression or transfer molding processes to make numerous articles for industrial, technical and novelty uses and for other applications.

As, modifying gents various fillers may be used, for example wood flour, alpha flock, sand, asbestos, mica, paper, cloth, cellulose derivatives such ascellulose itself; cellulose others; natural and" syntheticfilamentsor fibers, etc., in continuous, shredded or comminuted form. ,r:'igments, dyes, opacifiers,yplastici zing substances such as dibutyl phthalate, esters of monobasic and polybasic acids, etc., may be incorporated into the copolymers of this invention to modify the same. Natural and synthetic resins, gums, oils, waxes, polyhalogenated aromatic deriva ti ves, etc., likewise may be added .as modifying agents. {r i ln-a solvent, ;or withouta solvent utilizing a melt process, the fusible or soluble compositions may be used in adhesive and laminating applications to bond paper, wood, mica flakes, glass sheets, rubber sheets, etc., fibrous materials such as silk, asbestos, glass fibers, synthetic fibers in filament, thread or fabric (woven or felted) form, etc., cellulose derivatives in sheet, comminuted or fiber form, etc. In the form of liquid coating compositions such as lacquers, enamels, varnishes, etc., they find application in surfaceprotective coatings, such as for walls, desks, wire, concrete, porcelains, etc. In a flowable condition without the use of solvents they may be used as impregnants for many porous bodies, such as cork, pottery, felts, or fabricated bodies with interstices, such as the windings of electrical coils, netted fiber, interwoven fibrous materials, etc.

From the foregoing description it will be seen that the present invention provides a method of producing new. synthetic compositions which comprises polymerizing a polymerizable compo-- sition comprising (1) a methylene malonic ester, more particularly an ester corresponding to the general formula coon where R represents an aliphatic or aromatic hydrocarbon radical, (2) a polymerizable unsaturated alkyd resin, and (3) a catalyst for accelerating the copolymerization of the materials oi! (1) and (2). The new synthetic compositions of this invention may be described as being compositions comprising the product of polymerization of a polymerizable mixture including (1) a methylene malonic ester, e. g., a methylene dialkyl malonate, a methylene diaryl malonate, and (2) an unsaturated alkyd resin, more particularly an unsaturated alkyd resin obtained by reaction of ingredients comprising a polyhydric alcohol, e. g., a dihydric alcohol, and an alpha unsaturated alpha beta polycarboxylic acid, e. g., an alpha unsaturated alpha beta dicarboxylic acid, the materials of (1) and (2) being copolymerizable. Specific embodiments of the invention include compositions comprising the product of polymerization of a polymerizable mixture 01 copolymerizable materials including (1) a methylene malonic ester, e. g., a methylene dialkyl malonate suchIfor instance, as methylene dimethyl malonate, methylene diethyl malonate, methylene dipropyl malonate, etc., and (2)a maleic, fumaric or itaconic ester of a polyhydric alcohol, more particularly a maleic, fumaric or itaconic diester of a dihydric alcohol. Also included within the scope of the present invention are compositions comprising the product obtained by copolymerization of ingredients comprising a glycol maleate, fumarate or itaconate, e. g., diethylene glycol maleate, while the said ingredients are admixed with a small amount of a polymerization catalyst, e. g., an organic peroxide. The products of the inven- 6 tionalso'include, compositions of matter comprisin an interpolymer of (1) a methylene malonic ester, more particularly a methylene maloniciesterv of an alcohol having at least three carbon atoms, e. g., methylene dipropyl malonate,

methylene dibutyl malonate, etc., and (2) at least one. polyhydric alcohol ester of analpha unsaturated alpha beta polycarboxylic acid, e.: g.,

a olyhydric alcohol ester of maleic,, fumaric or t co i acid. v I What I claim as new'and desire tosecureby Letters Patent of the United States is:

1. A polymerizable composition comprising (1) a methylene malonic ester, (2) a polymerizable unsaturated alkyd resin, and (3) a catalyst for accelerating the copolymerization of thelmaterials of (1) and (2).

.2. A composition comprising an interpolymer betadicarboxylic acid, said materials of (1) and (2) being copolymerizable.

5. A composition comprising an interpolymer of ingredients including (1) a methylene malonic ester and (2') a maleic ester of a polyhydric alcohol; said materials of (1) and (2) being copolymerizable. V

6. A composition comprising an interpolymer of ingredients including (1) a methylene malonic ester-and (2) a fumaric ester of a polyhydric alcohol, said materials of (1) and (2) being copolymerizable.

7. A composition comprising an interpolymer of ingredients including (1) a methylene malonic ester and-(2) an itaconic ester of a polyhydric alcohol, said materials of, (1) and (2) being copolymerizable. I a

8. A composition containing an interpolymer of copolymerizable materials including a maleic diester of a dihydric alcohol and a methylene dialkyl malonate.

9. A composition containing an interpolymer of copolymerizable materials including a fumaric diester of a dihydric alcohol and a methylene dialkyl malonate.

10. A composition containing an interpolymer of copolymerizable materials including an itaconic diester of a dihydric alcohol and a methylene dialkyl malonate.

11'. A composition of matter comprising an interpolymer of ingredients including (1) a meth" ylene malonic ester and (2) a maleic diester of a glycol, said materials of (l) and (2) being copolymerizable.

12. A composition of matter comprising an interpolymer of methylene dimethyl malonate and an unsaturated alkyd resin copolym'erizabletherewith. I v 1 13. A composition of matter comprising an interpolymer of methylene diethyl malonate and an unsaturated alkyd resin copolymerizable therewith.

mos-7:91

- 14.- A" composition of matter compri'sing'an 1nter-polyme'rof ingredientsincluding (1) a-methylene malonic ester of an alcohol having at least three carbon atoms and (2) a polyhydric alcohol ester of'anr alpha unsaturated'alpha beta poly carboxylic-acid, said materials of (1) and- (2) being copolymerizable.

15. composition comprising an interpolymer of ingredients comprising a" glycolrmalea t'e and a methylene dialkyl malonate copolymerizable 1'0 rials of (1) and (2).

therewith. H r

8. 16. As a new'product, an interpol'ymer of diethylene glycol maleate and 'a methylene 'dialk'yl malonat'e copolymerizable therewith;

- 1'1. The method of producing new synthetic compositions which comprises polymerizinga polymerizable= composition comprising (1) a methylene'malonic' ester, (2) apolymerizable unsaturated alkyd resin, and (3) a catalyst for accelerating the copolymeriza'tionof the mate- GAETANO' DALELIO'. 

